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10 April 2016, Volume 37 Issue 4

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Cover and Content of Chemical Journal of Chinese Universities Vol.37 No.4(2016)

2016, 37(4):  0-0. 

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Articles: Inorganic Chemistry

Preparation of Glass Ceramics Containing CaF₂ by One-step Method and Analysis of the Fluorescent Probe of Eu³⁺ Ion^†

WANG Caiping, LI Youfen, ZHANG Yidong

2016, 37(4):  607-612.  doi:10.7503/cjcu20160013

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Transparent glass-ceramics with composition n(SiO₂)∶n(Al₂O₃)∶n(CaO)∶n(CaF₂)∶n(NaF)∶n(B₂O₃)=40∶20∶10∶10∶15∶5 were fabricated via traditional melting technique with one-step method. X-ray diffraction(XRD) results of as-prepared glass-ceramics confirmed the existence of CaF₂ phase. Scanning electron microscopy(SEM) observation showed that the CaF₂ crystalline phase had a size of 200 nm and dispersed in the amorphous phase. The fluorescence intensity of glass ceramics was 1.7 times that of the glass. The emission spectrum showed several luminescence peaks at 590 nm(⁵D₀→⁷F₁), 614 nm(⁵D₀→⁷F₂), 652 nm(⁵D₀→⁷F₃) and 700 nm(⁵D₀→⁷F₄), which are attributed to the Eu³⁺ ion transition. The intensity ratio of ⁵D₀ -⁷F₂ transition to the ⁵D₀ -⁷F₁ transition and Ω₂ of Judd-Ofelt parameters were used to measure the rare earth ion site symmetry. The data revealed that Eu³⁺ ions are embedded into Ca-F environment from Si-O environment during the crystallization process. Therefore Eu³⁺ can be applied to investigate the microstructures of glass-ceramic crystal as a fluorescence probe.



Synthesis and Magnetocaloric Properties of Ni-Co-Zn Nano Ferrites^†

ZHAO Haitao, WANG Qiao, LIU Ruiping, MA Ruiting

2016, 37(4):  613-618.  doi:10.7503/cjcu20150952

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Ni_0.5-xCo_xZn_0.5Fe₂O₄ nanoferrites(x=0, 0.1, 0.2, 0.3 and 0.4) were synthesized via polyol process using triethylene glycol as the solvent and acetylacetonate metal salts as precursors. The structure, morphology and magnetic properties of the resultant particles were characterized by means of X-ray diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared spectrometry(FTIR) and vibrating sample magnetometry(VSM). The results show that Ni-Co-Zn nanoferrites have uniform size and good dispersibility. The monodisperse Ni_0.5-xCo_xZn_0.5Fe₂O₄ nanoferrites show a typical ferrimagnetic behavior at room temperature. The Ni_0.3Co_0.2Zn_0.5Fe₂O₄ nanoferrites have maximum saturation magnetization of 41.34 A·m²·kg^-1. The temperature of Ni_0.3Co_0.2Zn_0.5Fe₂O₄ nano ferrites suspension can reach up to 55 ℃ in alternating magnetic field, which reveals its sufficient magnetocaloric properties.



Analytical Chemistry

Synthesis of Triphenylamine Functional Dye for Highly Sensitive and Ultra-low Potential Photoelectrochemical Sensing of Glutathione^†

WU Shuo, XING Panpan, SONG Jie, ZHAO Yanqiu

2016, 37(4):  619-625.  doi:10.7503/cjcu20160003

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A triphenylamine functional dye(TCA) was synthesized and integrated with TiO₂ nanoparticles for the fabrication of photoelectrochemical(PEC) biosensors. The as-synthesized TCA with triphenylamine as an electron donor, thiophene as a π bridge and a carboxyl group as an electron acceptor possessed high molar absorption coefficient in visible light region, suitable excited state energy level and good excited state stability, as well as strong coordination ability with TiO₂ nanoparticles. Taking advantages of these merits, the TCA is bounded on TiO₂ nanoparticle and modified on the surface of fluorine doped tin oxide electrode(TCA-TiO₂/FTO). The obtained TCA-TiO₂/FTO electrode showed a photocurrent response at 0 V to a light excitation of 480 nm, which could be further enhanced through an oxidation process of biomolecules by the hole-injected TCA. Using gluthathione as a model analyte, a sensing strategy for sensitive PEC biosensing at an ultra-low potential and under irradiation of visible light was developed. Under optimal conditions, the PEC biosensor shows good linear relationships with GSH concentration in the ranges of 2 to 100 μmol/L and 0.1 to 2.4 mmol/L, with a detection limit of 1.0 μmol/L. This PEC biosensing platform offers an alternative method for monitoring biomolecules and provides a new strategy to design PEC biosensors with organic dyes.



EESI-MS Detection and Statistical Analysis of Multi-batch of Exhaled Breath Metabolomics Data of Liver Failure Patients

LI Penghui, DENG Lingli, LUO Jiao, LI Wei, NING Jing, DING Jianhua, WU Xiaoping

2016, 37(4):  626-632.  doi:10.7503/cjcu20150826

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In metabolomics studies, the number of samples should be enough to guarantee the reliability of data statistical analysis. The effective storage time of exhaled breath is short, and it is difficult to collect and detect a large number of breath samples in a short time. Combining multi batches of samples may obtain a large data, but usually there is a large variance between batches induced by ambient air varying. In this paper, the exhaled breath data of liver failure patients and healthy volunteers were obtained by high resolution extractive electrospray ionization mass spectrometry(EESI-MS) and then analyzed by multi-block partial least square(MB-PLS). The results were compared with traditional PLS method and showed its strength of removing the variance of batches for modeling. Moreover, we provided a variable selection strategy that based on variable importance in the projection(VIP) of MB-PLS to reduce the redundancy of data and eliminate the effect of non-information variables for modeling, and the performance of MB-PLS model had a great improvement.



Simulation of the Formation and Fission of Charged Droplets in Electrospray Ion Source^†

HUANG Zhaoliang, GAO Fangyuan, WANG Boliang, ZHANG Weibing

2016, 37(4):  633-637.  doi:10.7503/cjcu20150812

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The Fluent software was used to simulate the formation and fission of charged droplets in electro-spray ion source based on the transport behavior of liquid in electrospray ion source(ESI) and constructed. The influence of the capillary voltage, ion source temperature and surface tension on droplet size distribution was studied. The results indicate that high capillary voltage, high source temperature, and low surface tension lead to smaller charged droplets and better breakup, which is in consistency with the study in published literatures and the calculation with empirical formula in this work.



Two-photon Fluorescent Labeling Kit for the Real-time Dynamic Biopsy of CA19-9^†

HUANG Chibao, ZHANG Daohai, ZENG Boping, LIU Qibin, CHEN Huashi, KANG Shuai, CHEN Xiaoyuan

2016, 37(4):  638-642.  doi:10.7503/cjcu20150727

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Carbohydrate antigen CA19-9(Ag) is a tumor marker associated with pancreatic cancer, gallbladder cancer, colon cancer and gastric cancer in early stage of tumor and cancer stage. Antibody Ab19-9(Ab) to carbohydrate antigens were labeled to form probe-labeled antibody LP-Ab using the prepared two-photon fluorescence probe LP. On the basis of the antigen-antibody specificity affinity principle, LP-Ab could combine with carbohydrate antigen Ag into a complex LP-Ab·Ag, which was excited by near infrared laser(740 nm) and emitted strong two-photon fluorescence to accomplish the high sensitive biopsy and real-time dynamic high-resolution imaging of the tumor marker Ag with two-photon fluorescence microscope. Based on this, a simple and convenient two-photon fluorescent labeling kit was prepared to realize the rapid detection of tumor, which is convenient for large-scale clinic testing and screening. The research further broadens the application of LP, and provides a sharp tool for revealing the mechanism of cancer occurrence, development and metastasis. LP-Ab can be used to observe and study the dynamic transfer mechanisms of the tumor markers in cells and the mechanism of carcinogenesis.



Ratiometric Fluorescent Probe for the Detection of Glutathione in Living Cells^†

YANG Runjie, TANG Yao, ZHU Weiping

2016, 37(4):  643-647.  doi:10.7503/cjcu20150725

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A fluorescent probe(4) for the detection of biothiols was designed and synthesized and its properties for labeling glutathione was investigated. After reaction with glutathione in 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid(HEPES) buffer, the color of solution changed from light yellow to pink, which could be detected by naked eyes. Meanwhile, the fluorescence was enhanced at 608 nm. Probe 4 was useful for measuring glutathione at concentrations ranging from 1.6×10^-5 to 2×10^-4 mol/L with a detection limit of 8.9×10^-7 mol/L. Besides, probe 4 was sensitive to glutathione in MCF-7 cells, which emitted red fluorescence when it was incubated with MCF-7 cells.



Microfluidic Analysis System Integrated with Liquid-liquid Extraction and Liquid-liquid Waveguide^†

JIANG Jian, LI Panpan, MA Yingxue, YANG Chunguang, XU Zhangrun

2016, 37(4):  648-653.  doi:10.7503/cjcu20150701

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A microfluidic analysis system integrated with liquid-liquid extraction and liquid-liquid waveguide detection was explored. Multiphase laminar liquid-liquid extraction was realized using 1-butyl-3-methyl imidazolium bromide ionic liquid/sodium carbonate solution aqueous two-phase system. Liquid-liquid waveguide absorption photometric detection was achieved by the ionic liquid with higher refractive index served as liquid core and the salt aqueous solution with lower refractive index served as liquid cladding. The extraction efficiency for cresol red extraction is more than 93%. The linear range, the relative standard deviation and the detection limit for cresol red detection were 0.01—0.40 mg/mL, 3.4%(n=11) and 3.8 μg/mL(3σ) respectively. Extraction separation and liquid-liquid waveguide-based long optical path absorbance detection were integrated in the system, which provided a new strategy for expanding the application of absorbance detection in microfluidic systems.



Rapid Discrimination of Chemotypes of Cinnamomum camphora by Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry^†

LIU Xingxing, FANG Xiaowei, HUANG Xueyong, ZHANG Tingting, CHEN Huanwen, LUO Liping

2016, 37(4):  654-660.  doi:10.7503/cjcu20150684

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Surface desorption atmospheric pressure chemical ionization mass spectrometry(SDAPCI-MS) was selected to detect five chemotypes of C. camphora leaves powder and the raw mass spectral fingerprints of the powder samples were obtained. Principal component analysis(PCA), cluster analysis(CA) and the back propagation artificial neural network technology(BP-ANN) were used to analyze the spectral information. The results showed that the SDAPCI-MS technique could got mass spectral fingerprints of C. camphora quickly in positive ion mode. The contribution rates of PC1, PC2, PC3 were 79.9%, 12.9% and 4.2%, respectively, with a total of 97.0% in PCA. The accuracy of discrimination of CA and BP-ANN of SDAPCI-MS was 100%.



Organic Chemistry

Synthesis and Antitumor Activity of Targeting and Nano Drug-Carrying Micelles Mediated by Rabies-virus-derived Peptide RVG29

HAN Hailing, JIN Shunzi, MIAO Zhuang, CHEN Ping, WANG Zhanfeng, XIE Zhigang

2016, 37(4):  661-668.  doi:10.7503/cjcu20150941

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Starting with water soluble dextran(Dex), paclitaxel(PTX)-carrying micelles M(PTX) and Rabies-virus-derived peptide(RVG29)-targeted and PTX-carrying micelles M(RVG,PTX) were prepared, by carboxylation of dextran and subsequently by conjugating PTX and RVG29 onto the carboxylated dextran. The products were characterized with nuclear magnetic resonance(¹H NMR) spectroscopy, transmission electron microscopy(TEM), and dynamic light scattering(DLS). The uptakes of the micelles by C₆ cells and the inhibition rates of C₆ cell growth by the micelles were measured by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide(MTT) assay, by confocal laser scanning microscopy(CLSM), and by flow cytometry(FCM). The results showed that molecular weight of Dex-PTX was about 16500 and that of RVG-Dex-PTX was about 19800. Micelles M(PTX) and M(RVG, PTX) assumed a shape of spheres with a diameter of 45-60 nm. The mass ratio of Dex, PTX and RVG29 was about 100: 20: 10. M(RVG, PTX) exhibited higher cell growth inhibition rate against C₆ cells than M(PTX) and C₆ cells took in more M(RVG,PTX) than M(PTX) under the same experimental conditions. When C₆ cells were treated with free RVG29 prior to cellular experiments, the inhibition rate against C₆ cells and the uptake by C₆ cells of M(RVG,PTX) were significantly decreased and came to a level of M(PTX). This implied that the enhanced inhibition of C₆ cell growth by M(RVG,PTX) and the enhanced uptake of M(RVG,PTX) by C₆ cells were mediated by RVG29, and the RVG29 species after conjugation with Dex reserved the targeting ability of RVG29 itself to a reasonable extent. Furthermore, in the preparation of M(RVG, PTX) micelles, only Dex was used as a carrier polymer, no hydrophobic polymer segments were involvd and there was no need of preparing drug-carrying copolymers and targeting copolymers, separately, and then doing co-assembling of them. In short, the manufacturing of M(RVG,PTX) micelles is relatively simple but they have the functions of drug-carrying and C₆-cell targeting, therefore, their practical application is expected.



Preparation and Suzuki Reaction Performance of Pectin-supported Palladium Catalyst^†

ZHOU Wenjun, ZHOU Yu, ZHANG Xiazhong, ZENG Bin

2016, 37(4):  669-673.  doi:10.7503/cjcu20150799

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To discover new heterogeneous palladium catalyst in organic synthesis, pectin, which was extracted form citrus peel, was used as supporter for the preparation of pectin-supported palladium catalyst. The pectin-supported palladium catalyst was applied to Suzuki cross-coupling reaction between sodium tetraphenylborate and aryl bromides. The results revealed that all four aryl groups of sodium tetraryylborate could be efficiently utilized in the Suzuki cross-coupling reactions in an atom-efficient way in the presence of Et₃N as base in PEG 400/H₂O at 110 ℃ in open air, providing excellent yields of the corresponding functionalized biaryls within 1 h. The present protocol has the advantages highly efficient, high yield, mild condition, short reaction time, as well as the catalyst can be recycled and reused.



Theoretical Studies on Tetragonal, Monoclinic and Orthorhombic Distortions of Germanium Nitride Polymorphs^†

CANG Yuping, CHEN Dong, YANG Fan, YANG Huiming

2016, 37(4):  674-681.  doi:10.7503/cjcu20150921

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Applying the ab initio pseudo-potential technique, we had predicted the lattice structures, density of states, phonon dispersion curves of the recently-discovered tetragonal, monoclinic and orthorhombic phases of Ge₃N₄. The negative formation enthalpy, the satisfactory of Born’s stability criteria and no imaginary frequency can be seen in the phonon dispersion curves proof that the three Ge₃N₄ polymorphs can retain their stabilities in the pressure range of 0―20 GPa. The temperature affects the cell volume, thereby decreasing the bulk modulus. The band gaps show that Ge₃N₄ are semiconductors, while obvious s-p hybridizations can be seen in the density of states. The band gaps decrease with applied pressure, which is due mainly to the generation of non-local electrons. Then, the quasi-harmonic approximation is used to study the thermodynamic properties of Ge₃N₄. The results show that the thermal expansion coefficient, entropy, heat capacity, Debye temperature and Grüneisen parameter are significantly affected by both temperature and pressure. The thermal expansions of m-Ge₃N₄ and t-Ge₃N₄ are three and two times greater than that of o-Ge₃N₄, respectively. The lattice vibration frequency of o-Ge₃N₄ keeps unchanged at different temperatures. Our results are concordant with the experimental data and the previous results. Therefore, the present results indicate that the combination of ab initio calculations and quasi-harmonic approximation is an efficient method to simulate the high-temperature behaviors of different Ge₃N₄ polymorphs. Generally speaking, the results listed in this work are all predictions, which need to be verified by experiments in the near future.



Physical Chemistry

In situ Formed Au Nanolayer as a Bifunctional Catalyst for Li-air Batteries^†

ZHANG Lei, LIU Qinghua, DUAN Xiaobo, HUA Xiaohu, ZHU Ding, CHEN Yungui

2016, 37(4):  682-687.  doi:10.7503/cjcu20150882

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Au nanolayers(ANL) were in situ formed on the Ni foam(SP) via the galvanic exchange method. The as-prepared ANL/SP was applied as the current collector of air cathode for the Li-air battery which operated in pure O₂, ambient air and simulated air. The electrochemical performances of ANL/SP electrode for Li-O₂ battery were investigated. The results showed that the in situ incorporation of ANL significantly improves the energy output and the cycling performance of the aprotic Li-O₂ battery in ambient or simulated air, and effectively facilitates the oxygen reduction/evolution reactions(ORR/OER) kinetics of the O₂ electrode in simulated air.



Dehydrogenation Property and Mechanism of 3LiBH4/CeF3System

GU Run, ZHANG Ming, WANG Chunyang, HUANG Weijun, LIU Dongming

2016, 37(4):  688-692.  doi:10.7503/cjcu20150848

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The 3LiBH₄/CeF₃ reactive system was prepared by ball-milling treatment. Its dehydrogenation property and reaction as well as the property improvement mechanism were investigated by pressure-composition-temperature(PCT) analyser, X-ray diffractometer(XRD) and Fourier transform infrared spectrometer(FTIR). It was found that the 3LiBH₄/CeF₃ system fast released hydrogen at about 295 ℃ with about 4.1%(mass fraction) of hydrogen totally desorbed. During the dehydrogenation process, CeF₃ reacted directly with LiBH₄ according to the reaction 3LiBH₄+CeF₃ 1/2CeB₆+1/2CeH₂+3LiF+11/2H₂. In comparison with pristine LiBH₄, the decrease in dehydrogenation thermodynamic stability and apparent activation energy are the main reasons for the declined dehydrogenation temperature of the 3LiBH₄/CeF₃ system.



Adsorption and Selective Hydrogenation Mechanism of Crotonaldehyde on AuSurface

JIANG Junhui, XIA Shengjie, NI Zheming, Zhang Lianyang

2016, 37(4):  693-700.  doi:10.7503/cjcu20150844

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The stabilities of four possible configurations for crotonaldehyde were investigated with density functional theory(DFT) model. The most favorable configuration of crotonaldehyde was selected to explore the adsorption and its selective hydrogenation mechanism on the Au(111) surface was also investigated. The calculated results showed that the E-(s)-trans-crotonaldehyde was the most stable configuration. The adsorption at the top site was most stable when the crotonaldehyde on the Au(111) surface with CO. And its adsorption energy was maximum. The d orbitals of the metal surface interact strongly with the p orbitals of the crotonaldehyde. And the crotonaldehyde losed 0.045 electrons after adsorption on the Au(111) surface. In addition, comparing the reaction energy, activation energy and structure change of each elementary steps, we obtained that the crotonaldehyde was more likely to follow the 2,1-addition mechanism(partial hydrogenation mechanism) to produce crotyl alcohol, and the lower temperature was helpful for the reaction to improve the conversion rate.



Preparation and Electrocatalytic Properties of Metal Oxide-coated Titanium Anodes Used in Low-temperature Seawater^†

WANG Rui, WANG Tingyong, XU Haibo

2016, 37(4):  701-705.  doi:10.7503/cjcu20150795

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Ti/(Ti-Ta_x)O₂/IrO₂ anodes with middle coating were made by thermal decomposition at different temperatures, while the middle coating was made from a mixture of TaCl₅-butanol saturated solution with TiN nano-powder. Compared with the traditional Ti/IrO₂ anodes, these new anodes were characterized by X-ray diffraction(XRD) and scanning electron microscope(SEM), and studied by electrochemical measurements such as polarization curve, cyclic voltammetry and acce-lerated life test. The results revealed that for Ti/(Ti-Ta_x)O₂/IrO₂ anodes calcinated at 400 ℃, the addition of middle coating acquired a much better IrO₂ crystallization at the surface and a cracked-mud morphology which was usually obtained at high temperature. Furthermore, compared with the anode calcinated at 500 ℃, the electrocatalytic activity of the anode prepared at 400 ℃ was highly raised, its electrochemical active area was increased by 6 times, and the working potential was decreased by 100 mV(to 1.37 V) at a current density of 100 mA/cm² in 4 ℃ seawater. Meanwhile, the accelerated life was increased by 10 times, compared with the Ti/IrO₂ anode prepared by traditional method. Therefore, the newly developed anodes are suitable to be used in low-temperature seawater with good electrocatalytic property and stability.



Virtual Screening of Small Molecular Stabilizer for Y220C Mutant of p53^†

DING Jiyong, SHEN Hongchen, LIU Fufeng

2016, 37(4):  706-714.  doi:10.7503/cjcu20150790

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About half of cancers are caused by the mutation in the tumor suppressor p53. A hydrophobic cavity on the surface of p53 was caused by the Y220C mutation. The surface crevice is on the opposite side and distant from the DNA-binding domain, making it a particularly attractive target site for stabilizing small-molecule drugs. In order to obtain the effective stabilizers, Lipinski’s rule of five, twice docking methods and molecular dynamics(MD) simulations were successively used for virtual screening the DrugBank 4.0 library and tacrine was obtained as a candidate stabilizer. Then, all-atom MD simulations were used to verify the affinity between tacrine and the target protein. The MD simulation indicated that tacrine bound tightly to the pocket and the complex remained stable. The affinity between tacrine and the target protein was further analyzed. It was found that the hydrophobic and electrostatic interactions dominated the affinity between tacrine and the target protein. And, the hydrophobic interactions were dominant force. Moreover, there were 3 hydrogen bonds between tacrine and the residues Leu145, Val147 and Asp228 of p53C-Y220C. And then, the detailed binding process of tacrine and p53C-Y220C was probed based on MD simulations. Finally, the stabilizing capacity of tacrine on p53C-Y220C was further validated by thioflavine T fluorescent experiments.



Preparation of Biocompatible Protein-hydrogel-based Micro-patterns via UV Lithography^†

ZHENG Boyuan, JI Fengying, HOU Zhishan, SUN Siming, SUN Yunlu, YANG Ruizhu

2016, 37(4):  715-722.  doi:10.7503/cjcu20150733

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Through facile UV lithography, without chemical modification, biocompatible natural protein-hydrogel-based film and micro-patterns were prepared. The micro-patterns can be used as micro-grating optical devices. Then rainbow feature was observed and diffraction fringe for a 638 nm laser beam was obtained under white light, even with a diffraction level up to 11. Further more, micro-wrinkles could be controlled by changing related parameters. Finally, HepG-2 cells were cultured on the protein micro-patterns and cell micro-patterns were obtained.



Hydrogenation of 4-Nitrophenol over MIL-101 Confinement Au Nanoparticles Catalyst^†

WANG Kai, XU Li, CHEN Hengze, QIAO Huiying, CHEN Chao, ZHANG Ning

2016, 37(4):  723-727.  doi:10.7503/cjcu20150691

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A series of Au@MIL-101 catalysts with good catalytic activity was prepared. The X-ray powder diffraction (PXRD), transmission electron microscopy (TEM), physical adsorption and atomic emission spectroscopy (AES) were used to characterize and analyze the catalysts. The 0.29%Au@MIL-101 catalyst displayed a good catalytic activity for 4-nitrophenol reduction under mild reaction conditions.



Changes of Structure and Functional Group of Reduction of Graphene Oxide with p-Phenylene Diamine^†

ZHAO Xiaolong, SUN Hongjuan, PENG Tongjiang

2016, 37(4):  728-735.  doi:10.7503/cjcu20150682

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The p-phenylene diamine(PPD) were selected as reducion and modification agent to prepare functionalized and reduced graphene(GOP-X) by one-step simple refluxing method. Infrared spectrum(FTIR), X-ray photoelectron spectroscopy(XPS), X-ray diffraction(XRD) and UV-Vis absorption spectrum were used to investigate the reaction types and structure changes between PPD and graphene oxide(GO). The results show that the d-spacing of GOP-X layers increases firstly and then decreases with the increase of X(the mass ratio of PPD and GO), and the conjugated structure gradually restored; when the solvent molecular interaction, the amplification of the d-spacing decrease to a steady figure. Three types of bonds between PPD and GO were proposed: (Ⅰ) hydrogen-bonding interaction between the oxygen-containing functional groups of GO and the PPD molecules(C—OH…H₂N—X); (Ⅱ) ionic bonding in protonating amine by the weakly acidic sites of the GO layers(—COO^-\begin{array}{c}{H_3}^{+}\end{array}N—X); (Ⅲ) covalent bonding from amidation and nucleophilic addition reactions between the amie in PPD(NH₂ ) and the oxygen containing groups of GO. Furthermore, the NH₂ prefers to react first with the carboxyl group(COOH) and then with the epoxide group(C—O—C), and the relative action mechanisms were also described.



Catalytic Properties of Fast Pyrolysis Char Loaded with Cu-Zn on Alkali Lignin Pyrolysis for Monophenols^†

WANG Wenliang, GENG Jing, LI Lufei, CHANG Jianmin

2016, 37(4):  736-744.  doi:10.7503/cjcu20150681

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The fast pyrolysis char(FPC), which was a kind of mesoporous and macroporous carbon materials, was loaded with different molar ratios of Cu and Zn using the co-impregnation method to prepare the catalysts of Cu_xZn_y/FPC. The catalysts were characterized by X-ray diffraction(XRD), field-emission scanning electron microscope(FE-SEM) and energy dispersive X-ray spectroscopy(EDX). The catalytic properties on generating monophenols from alkali lignin pyrolysis were determined by thermogravimetric analyzer(TG) and pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS). The results showed that the active components of CuO and ZnO were homogeneously embedded into the mesoporous and macroporous structure of FPC without the occurrence of aggregation or copper zinc alloy. With the metal loading increased, the diffraction peak intensity of CuO and ZnO was enhanced and average crystal sizes of CuO and ZnO became larger gradually. TG analysis showed that the catalysts significantly improved the reaction efficiency by reducing the activation energy while inhibited the formation of char residues. The monophenols obtained from the catalytic pyrolysis of alkali lignin were simplified from 23 kinds to 10 kinds. The catalyst of Cu_0.67Zn_0.33/FPC had the highest selectivity of monophenols up to 52.99%, and the selectivity increased by 49.7% compared with the catalyst of Cu/FPC.



Preparation of Ce Modified Mg-Al Mixed Metal Oxides by Aqueous Reconstruction for Vapor Self-condensation of Acetone^†

WU Binquan, WANG Sheng, HUANG Liang, QIN Feng, HUANG Zhen, XU Hualong, SHEN Wei

2016, 37(4):  745-751.  doi:10.7503/cjcu20150653

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Ce modified Mg-Al mixed metal oxides(HTc-Ce) were prepared by aqueous reconstruction method. The construct and surface properties of catalysts were characterized by X-ray diffraction(XRD), X-ray photoelectron spectrometry(XPS), transmission electron microscopy(TEM) and N₂ adsorption and desorption isotherms. Aqueous reconstruction process promotes forming more defects on the Mg-Al mixed oxides, Ce is successfully embedded into the interlayer of hydrotalcite framework and enlarges its spaces, which improves the accessibility of active sites. The oxygen mobility of ceria increases the amount of basic sites on the surface. XPS results indicate that there is about 30% of Ce(Ⅲ) in cerium oxides. Oxygen vacancies are beneficial to enhancing the ability of oxygen mobility. In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) verifies the augment of low-coordinated oxygen, CO₂-temperature programmed desorption(CO₂-TPD) experiment reveals that modification of Ce increases the density of basic sites on surface. Aqueous reconstructed HTc-Ce-3.2 catalyst exhibits high activity for acetone self-condensation. The conversion of acetone is 56.8%. It is 2.5 times higher than that of HTc catalyst, the selectivity of pentamers enhance significantly.



Polymer Chemistry

Synthesis and Characterization of Polyampholyte Hydrogels Based on Hyperbranched Polymer^†

WANG Haiwei, LIANG Xuechen, XU Kun, TAN Ying, LU Cuige, WANG Pixin

2016, 37(4):  752-760.  doi:10.7503/cjcu2015956

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The cationic hyperbranched oligomer poly(N-acryloyl-1,2-diaminoethane hydrochloride)(HADE) was firstly synthesized by Michael addition reaction. And then, polyampholyte hydrogels(HAH gels) with good mechanical strength were prepared with HADE as macromonomer, acrylamide(AAm) and acrylic acid(AAc) as comonomers in the absence of chemical crosslinking agent. The results of mechanical testing showed that HAH gels could sustain compressive strain of 99% without breaking and the optimized compressive strength was up to 61.2 MPa. And they also could be stretched over 1700% and tensile strength was 70.2 kPa in tensile test. During the fabrication of HAH gels, amino free radicals derived from the oxidation-reduction reaction between amino groups of HADE and oxidation initiator and double bonds on the end of HADE could simultaneously participate in copolymerization with AAm and AAc. Therefore, HADE could be considered as a chemical cross-linking agent. Meanwhile, physical cross-linking action originated from static-electronic inte-raction between cationic amino groups of HADE and anionic carboxyl groups of AAc could also improve the mechanical performance of HAH gels. Thus, HAH gels could exhibit excellent mechanical performance due to the synergetic effect of chemical and physical cross-linking action.



Band Broadening and Chain Conformation of Polyethylene Oxide by Gel Permeation Chromatography Coupled with Multi-angle Laser Light Scattering^†

LI Qi, ZHAO Wenjie, ZHAO Ziliang, JI Xiangling, BO Shuqin, LIU Yonggang

2016, 37(4):  761-766.  doi:10.7503/cjcu20150940

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The band broadening of aqueous gel permeation chromatography columns was studied by coupling with a multi-angle laser light scattering detector, using narrow polyethylene glycol(PEG) and polyethylene oxide(PEO) samples. The determined spreading factor of PEG/PEO increased with increasing molecular weight between 4.0×10³ and 1.3×10⁶. True molecular weight distributions of these samples were obtained with band broadening correction. Despite the presence of band broadening in the columns, the monodisperse scaling law between radius of gyration and molecular weight of PEO is established to be R_gz=0.0272 \begin{array}{c}{M_w}^{0.56}\end{array}, indicating that the long PEO chains take a swollen random coil conformation in water due to the presence of excluded volume effect.



Tuning of Ionic Interaction and Rheological Properties of Nanoscale Ionic Materials^†

LIU Yangjian, RUAN Yingbo, ZHANG Baoqing, QIAO Xin, LIU Chenyang

2016, 37(4):  767-774.  doi:10.7503/cjcu20150856

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We prepared two kinds of silica-based nanoscale ionic materials(NIMs) with increasing SiO₂ contents, and also with different relative ionic interaction strengths between their constituents(SiO₂-SIT-M2070>SiO₂-SIT-Ethomeen for the relative ionic interaction strength). The results of transmission electron microscope(TEM) and small-angle X-ray scattering(SAXS) investigations indicated that there was no obvious nano-particle aggregate in both kinds of NIMs. The differential scanning calorimetry(DSC) results showed that the ionic interactions prohibited the crystallization of out-shell block copolymers in the prepared NIMs. Moreover, the crystallization suppression was more serious with increasing the ionic interaction strength. Ionic interaction also displayed the dramatic influence on the dynamic rheological behavior of as-prepared NIMs. The dynamic shear moduli and viscosities of SiO₂-SIT-Ethomeen were about 1—3 orders of magnitude lower than those of SiO₂-SIT-M2070 with the same solid contents. Under the shear of large dynamic strain, SiO₂-SIT-M2070 with the relatively high solid contents showed the soft glass rheological properties, while SiO₂-SIT-Ethomeen showed the phenomenon of strong strain overshoot. Furthermore, the strain that corresponding with the maximum of dynamic shear moduli and viscosities gradually decreased with the increasing of solid contents, and so did the degree of overshoot. All above results suggested that the rheological properties of NIMs could be effectively controlled by carefully tuning the ionic interactions between their constituents.



Crystallization Behavior of Nanostructured Poly(vinylidene fluoride)/1-Vinyl-3-butylimidazolium Chloride Ionic Liquid Composites^†

XING Chenyang, WANG Yanyuan, LI Yongjin, LI Jingye

2016, 37(4):  775-780.  doi:10.7503/cjcu20150822

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The effect of poly(vinylidene fluoride)-graft-(1-vinyl-3-butylimidazolium chloride [VBIM][Cl])(i.e. PVDF-g-[VBIM][Cl]) nanodomains on the crystallization behavior in nanostructured PVDF/[VBIM][Cl] composite was investigated by means of differential scanning calorimeter(DSC), polarized optical microscope(POM) and wide-angle X-ray diffractometer(WAXD) measurements. ¹H nuclear magnetic resonance(¹H NMR) results confirm the successful grafting of [VBIM][Cl] onto the PVDF chains. Transmission electron microscopy(TEM) images show PVDF-g-[VBIM][Cl] nanodomains in the nanostructured PVDF/[VBIM][Cl](100/8, mass ratio) composite, which is distinct from the miscible PVDF/[VBIM][Cl] blend prepared by physically blending. The DSC results show higher crystallization temperature(T_c) and shorter crystallization time in the nanostructured PVDF/[VBIM][Cl] composite, compared with those of neat PVDF and PVDF/[VBIM][Cl] blend(100/8), respectively, indicating that nanodomains enhanced the crystallization rate of the PVDF crystals. Moreover, a larger nucleation density accompanied with smaller spherulites was observed in the nanostructured sample by POM photos. It is considered that strong thermodynamic incompatibility of nanodomains with PVDF matrix caused a large amount of partially ordered molecular chains at their interface, which favorites the nucleus formation and thus improves the entire crystallization rate of the PVDF crystals. Because of the confinement of [VBIM][Cl] within nanodomains, dominant non-polar α crystals were found in the nanostructured sample, which was the same with that of neat PVDF.



Preparation of Polyimide Nanofiber with Antimicrobial Activity by Electrospinning^†

ZHANG Futing, ZHOU Jinlong, HUANG Hairui, JI Zhenyan, YANG Liangjiong, FU Min, FANG Bijun, ZHANG Hongwen, JIANG Yan, YU Qiang, ZHOU Wanlin

2016, 37(4):  781-785.  doi:10.7503/cjcu20150821

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3,3',4,4'-Biphenyl tetra carboxylic diandhydride, 4,4'-oxydianiline and AgNO₃ were used to synthesis polyimide nanofiber with silver through two steps by electrospinning. The structure and morphology of nanofibers were studied by X-ray diffraction(XRD), transmission electron microscope(TEM) and scanning electron microscopy(SEM). The antimicrobial activity of polyimide(PI) and polyimide containing silver(PI/Ag) were researched through impregnation method. The results showed that silver’s crystal structure appeared in polyimide matrix, and silver particles, which average diameters were about 10 nm, dispersed uniformly on polyimide surface. The antimicrobial activities of PI/Ag nanofiber against E. coli, S. aureus and B. subtilis illustrated excellent effect and the best antibacterial rate up to 99.1%. This study may provide a new insight for polyimide applied in biomedical materials and other applications with good thermal performance and antibacterial property.



Preparation of Ru/Rh Bimetallic Nanoparticles Stabilized by Heterocyclic Poly(propylene imine) Dendrimer and Their Application for Catalytic Hydrogenation of Nitrile-Butadiene Rubber^†

XIAO Ye, WANG Yang, ZHOU Wei, PENG Xiaohong

2016, 37(4):  786-792.  doi:10.7503/cjcu20150797

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A series of Ru/Rh bimetallicdendrimer-stabilized nanoparticles[Gn-M(Ru_xRh_100-x) DTNs, x: mole molar fraction of Ru] was prepared by complexing-reducing method with the 15-membered azamacrocycles-terminated poly(propylene imine) dendrimer(Gn-M, n=2, 3, 4) as template. These bimetallic DTNs were used as catalysts for the hydrogenation of nitrile-butadiene rubber(NBR). The results of UV-Vis spectroscopy(UV-Vis), X-ray diffraction(XRD) and energy dispersive spectrum(EDS) indicated that bimetallic ions were successful reduced and stabilized by Gn-M. Particle size analysis showed that the average size of G2-M(Ru₅₀Rh₅₀), G3-M(Ru₅₀Rh₅₀) and G4-M(Ru₅₀Rh₅₀) DTNs were 7.5, 8.1 and 4.5 nm, respectively. G4-M(Ru₃₀Rh₇₀) DTNs catalyst reached the maximum hydrogenation degree(HD) of 99.51%, and the results of gel fraction measurement and ¹H nuclear magnetic resonance(¹H NMR) indicated that Ru/Rh DTNs were highly selective for the catalytic hydrogenation of NBR. Moreover, the HD can still reach 90.58% after twice recycle.



Preparation and Properties of Blend Proton Exchange Membranes Based on Side-chain Type Fluorine-containing Sulfonated Poly(ether sulfone) and Sulfonated Polyimide^†

TAO Yingyong, ZHANG Xulue, HU Zhaoxia, ZHANG Jingjing, GENG Hui, GAO Ying, YUAN Zufeng, BI Huiping, CHEN Shouwen, WANG Lianjun

2016, 37(4):  793-800.  doi:10.7503/cjcu2010560

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A series of blend membranes from a side-chain type fluorine-containing sulfonated poly(ether sulfone)s(sSPFES) and sulfonated polyimide(SPI) was prepared and characterized. The two sulfonated copolymers showed good compatibility in their trimethylamine salt form, producing uniform, transparent and ductile blend membranes during solution blending and casting processes. The resulting sSPFES/SPI blend membranes with ion exchange capacities in the range of 1.76—1.88 mmol/g showed some property differences in the water uptakes, size changes, proton conductivity and hydrolytic stability with the un-modified ones. Especially, their swelling behavior was considerable effected by the composition with obvious larger size changes in the membrane out-of-plane direction than the in-plane direction, exhibiting size changes no more than 10% in in-plane direction at 60 ℃ in water. The blend membranes could maintain rather good mechanical toughness after aging in water at 140 ℃ for 24 h with mass loss less than 6.1%. For the fully hydrated blend membranes, their proton conductivity all reached 0.1 S/cm at temperature above 50 ℃.